Composition of matter



Patented Feb. 9, 1937 v I v I UNITED STATES PATENT OFFICEG(.'iMIPOSI'.I.ION OF MATTER John H. Swanberg, Minneapolis, Minn.assignon,

by mesne assignments, to Koppers Company; a a A corporation of DelawareNo Drawing; Application January 1?; 1935 Serial No. 2,267

9 Claims. (Cl. 196152) This invention relates to a composition 01'matthis combination of substances as the flux for ten More particularlyit relates to a new type the tar. 1 of fluxed or cut-back tar productthat involves The hydrocarbons of the lighter fractions of the use 01 apetroleum distillate or other relapetroleum s 8 generally known,aliphatic 5 tively low-boiling aliphatic hydrocarbons and in nat 11 th hr h h mp unds 6 mixtures of hydrocarbons as the major fluxing compris nge mm n l weriling fractions agents for the tar. I or the petroleumdistillate such as gasoline, naph- It has long been the practice to fluxcoal tars t and k r se whi h are used in commerce and other tars withlower boiling oils of the same end y. Ve y n Chemical constitution 10chemical nature so that the tars could be applied which to a largeextent d pen s p n h o rce 10 at atmospheric temperature in certaintypes of t Petroleum, the refining Process and y v road construction andfor other purposes. Th additional treatments which they may have beenuse of the fluxed tar greatly facilitates theapgiven- If e Petroleumdistillate has not n plication and spreading of the tar especiallysubleeted o y Cracking Process in t cases where theris no source of heatavailable at the it will Consist p p y of Derefflnlc y e 15 site ofconstruction or application. After ape w h varying m nts 1 naphthenesand plication or the fluxed tar the flux is intended unsaturatcs s asflns- O a ly a petro to evaporate rapidly, leaving the original tar toleum distillate of this nature will contain only act as a bindingmaterial or protective coating. relatively small qua ti of o c ydro-Sometimes the usual types of tar distillate oils eerbons- In addition,large q es o asoavailable for fluxing actually do not evaporate1ihe,nephtha8 and lielesehes a being P d at sufliciently rapid rates andat such times the y cracking de pe r um and the i her use of mo rapidevaporating fluxes would boiling petroleum distillates. The percentageof advantageous. Lower-boiling aromatic oils such Da flin p nlUri-saturate d aroma ic 5 as benzene,'toluene, the xylenes or solventnaphcompounds in Such cracked P ts difier thas, are not used generallybecause of their high. d y, depending p the p 0! material cost. Theusual type of tar flux is often limited ac t t e of cr p ce s, the teminquantity. perature employed in the cracking process and Petroleumdistillates are available in large other c a y. th se p ducts from soquantities and at small cost. By taking'various c c prohesscs differ ompetroleum distilfractions of a petroleum distillate, fluxes of varylatesp d d ou cracking n t y ing evaporation rates are obtained; ,Thus, byuscontain Smaller amounts of p c p unds ing petroleum distillates asfluxes some of the d lar e ut vary g a un s i an n s diillcultiesencountered at times in the 'use 01' and unsaturates. Th aromaticcontent of such fluxed t are 1 t Manytypes of Detmcracked products isalso variable but usually is 35 leum distillates, however, are notcompatible with greater than that of on oncrockcd distillate a tar. Somepetroleum distillates, when added to at times isvconsidereble in extentw for tar, cause sludging to take place immediately in the Purpose ofthe Present invention the Demo the tar. Other petroleum distillates,while they leum distillates that are Particularly efen'ed to 40 domt'smdgetar immediately, do not form are those which contain principallythe parafflnic o ble solutions with the tar and separation takeshydrpcarbme William other combinatilms place in the mixtures onstanding. It is an obz prevent them from being compatible wit Ject ofthe present invention to make sible v the preparation of fluxed tarproducts whi l l will The boflmg range of the petroleum distillateremain stable and homogeneous for a long or other hydrocarbon oilsaliphatic in nature to 4-5 riqd of time containing petroleum distillatesor i usled m thehtar of a depeladent other relatively low-boilingaliphatic hydrocar arge y upon; 6 rate 0 evapom on desire A fiuxed tarhaving very quick setting-up properties b0 oils, having thecharacteristics mentioned a] fi as the major fl mg agent- This is can beobtained by using the type of petroleum distillate known to industrand'commerce as complished by mixing with petroleum distillate gasolineThis material wguld have an mmal material a. material of relatively lowboiling point boiling point of substantially 20 c, F.) to whichpredominates in compounds aromatic in substantially 60 C. F.) and amendpoint nature or having tar solvent characteristics simiof substantially0. (350 F.) to substantiallar to those .01 aromatic compounds and using1y 230 C. (450 F.). The specific gravity may 55 V Y i F.) tosubstantially 115 C. (240' F.) and an end point in a similar range asthat of the usual gasoline.

The range of the hydrocarbons may be increased if desired by usingkerosene which ordinarily includes the range of parafllnic hydrocarbonsfrom nonane to octadecane. A kerosene fraction of petroleum may overlapa gasoline fraction and vice versa. Kerosene generally dis.-

' tills from substantially 150 C. (302 F.) to sub-.

vent naphtha. either stantially 300 C. (570 F.) and its specific gravitymay be from substantially 31 Be. to substantially 48 Be. The combinedfractions of gasoline and kerosene give satisfactory results and in factany one of the lighter petroleum distillates or special fractionstherefrom may be used as conditions demand. Stoddard's solvent, apetroleum fraction, has been found to give improved results when used asdescribed in this invention. The initial boiling point of this lattermaterial is substantially 150 C. (300 F.) and its end point issubstantially 205 C. (400' F.) to 210 C. (410' IL).

v A wide variety of tar distillates and other'aromatic ofls may be mixedwith the petroleum distillate in order to make it compatible with tar.The desired result can be accomplished by the use of benzene, toluene orthe xylenes or a combination of these three. The product called solcrudeor refined, and boiling from substantially 100 C. to substantially 300C. can be used. The distillates from coke oven tar, horizontal retorttar, vertical retort tar, oil tars such as water gas tar, or acombination of any of these distillates may be used to advantage. Theboiling range of these distiliate's varies considerably at times, andsuch variations must be considered. Ordinarily these distillates haveinitial boiling pointsof substantially 150 C. to substantially 235 C.and in most cases at least 80 percent of the distillates will have beenremoved at a vapor temperature of 355 C. The predominatingcharacteristics of all these oils in the light of the present inventionis their .high'content of aromatic compounds and in fact, any aromaticoil boiling over a considerable range between 80 C. and 400 C. with themajor portion of the distillate boiling below 300 C. can be used tobring about the desired result. In addition, close cut fractions orindividual compounds taken from these .oils may be used to advantage.pounds should not have boiling points substantlally greater than 300 C.

However, the material petroleum distillate is not limited to tardistillates or aromatic oils and compounds. The petroleum industry is,by the use of new refinin processes and chemical treatments, developingnew solvents and fluxes which have solvent characteristics very similarto those of the aromatic oils. Certain of these oils, such as thehydrogenated naphthas, or special fractions thereof, may be used toadvantage to accomplish theobjects of the present invention. Up to. thepresent time, however, no specially treated 9 11mm In such cases thefractions or comtobeusedwiththeproduct has been developed that has thesame efilciency as the better aromatic oils for modify ing thecharacteristics of the untreated petroleum distillate.

Various tars and types of tars may be fiuxed by means of the new fiuxset forth above. The invention may be used to advantage with both hightemperature coke oven tars and low temperature tars. Other coal tarsthat may be used include blast furnace tar, horizontal retort tar. andvertical retort tar. Other types of tars such as water--gas tars and oilgas tars including residual tars, residuum tar, Bunker C tar and'Pintsch gas tar or mixtures ofanyoi these tars and other tars may beused. By residuum tars -or residual tars is meant the condensatesresulting from pyrogenous treatment of residual oils, for example,cracker residues, in gas manufacturing processes. Each of these tars, onthescribed herein can be used to advantage with these tar-asphaltcombinations also.

A number of procedures-have been developed to change some of thecharacteristics of tar in order to meet certain economic exigencies andconstruction problems. It is the custom, at times. to add certainmaterials. designated in the industry as "fillers" such as. powderedcoal, lampblack, limestone dust. or similar materials, to

the tar, thereby modifying its characteristics to some extent byincreasing the solids content. Other procedures involve the partialoxidation of the tar by air blowing or by treatment with oxidizingchemicals at various temperatures in order to obtain a bituminousmaterial having certain special characteristics. Such oxidations involvenot only the oxidation of the tar itself but also the partial oxidationof a tar oil by such means as Just described, the partially oxidized oilthen being combined with a tar pitch to produce a bituminous materialhaving special characteristics. Special tars are prepared at other timesby adding tar oils of certain boiling'ranges such 1 as creosote oils orits fractions to the tar, either crude or refined, so as to bring aboutchanges in the characteristics of the tars. Other special tars areprepared by distilling the tar to a pitch and thendissolving the pitchin'tar ofls having certain boiling ranges such as creosote oils or itsfractions. The tar oils mentioned in the last three cases are not to .beconsidered as fluxes because ordinarily their boiling ranges are abovethose of fluxing oils. In other cases, tars of higher consistency aresometimes obtained by adding pitch to the tar, either crude or refined..At times, the tar residuals obtained from the hydrogenation of tar orits derivatives or products of similar chemical nature may be used forconstruction pared from any of the above mentioned tars or combinationof tars or tar-asphalt mixtures intended for use in manufacturing fluxedmate rials varies considerably depending upon the purpose for which thefluxed material is intended. In the case of a road primer, a light taror somewhat viscous tar may be used as the base, enough flux being addedto obtain a material having a predetermined viscosity. For the sur--there may be included either hard or soft pitches.

The new flux described herein can be used to advantage in any of thesecases.

It is obvious, from the many factors involved, that no exact figures canbe given for the proportions of petroleumdistillate or similar oils toaromatic or similar oils, but that the proportions will vary with theproblems to be solved and conditions at hand. The proportion willdepend, flrst, upon the type and nature of the petroleum.distillateused. A petroleum distillate containing a high percentage ofparamnic compounds and a small'percentage .of aromatic compounds willrequire a larger amount of aromatic oilsv than a petroleum distillatecontaining a somewhat smaller percentage of paraflinic compounds and afair percentage of aromatic compounds. The type of tar will have someinfluence. In addition to the 'type of tar, the consistency of the tarhas influence on the proportion; this is so because the lower boilingaromatic compounds in the tar base itself have an effect on thestability and homogeneity of the petroleum distillate-fluxed tar. Forinstance, the flux for a light tar base intended for road priming willnot require as high a percentage of aromatic oils to be added to thepetroleum distillate as a flux to of the cases studied it was found thata larger proportion of a certain type of solvent naphtha was requiredwith a certain petroleum distillate than of a certain type of coal tarneutral oil with that same petroleum distillate in order to obtaincomparable results. However, the source and characteristics of thedifierent usable types of oils are so variable that it is not possihleto state definitely that any one type is superior to the rest, but ingeneral an aromatic oil with an appreciable percentage distilling tosubstantially 300 C. may be expected to be slightly better than a lowerboiling aromatic oil. 4

Aside from the variables introduced by the chemical and physicalcharacteristics of the materials involved there are other factors thatmay be of influence in determining the ratio of petroleum distillate toaromatic oils. In some cases satisfactory mixtures could be obtainedusing 5 parts of tar oil and 95 parts of petroleum distillate as flux,butat the same time it was somewhat difficult to eflect mixing, acontinued mixing action and relatively high temperature being necessary.In some cases it may be more practical to increase the proportion ofaromatic oils to some extent over the minimum point and thereby make theblendingoperation less diilicult. 'In other cases where economics andavail-- ability of tar oil distillates are of more importance than therate of set-up of the fluxed tar the proportions of aromatic oil may bevaried above the minimum point to suit the conditions. In such cases acommercial gasoline may be used and the proportion of higher boilingaromatic oils can be adjusted above the minimum point so that the fluxedtar can meet certain specifications as to flash point.

In case of petroleum distillates which, by

themselves, cause formation of sludge in tar, the

following blending procedure may be advanta-' geous. The petroleumdistillate is mixed with the aromatic oil such as described above andthen the resulting product is mixed with the tar to be fluxed. In caseswhere the petroleum distillate does not sludge the tar immediately butis not capable offorming stable and homogeneous mixtures with the tar itmay be more expedient to add the aromatic oil to the tar first therebyallowing it to be more thoroughly liquid at a lower temperature, thusreducing the fire hazard incident to the blending operation. In thissecond case, no particular procedure is deemed to causedimmediatesludging when added by itself to a tar. However, by mixing as low as 10parts by volume of water gas tar light oil with 90- parts by volume ofthis gasoline, a flux was obtained which formed a stable and homogeneousmix ture with the tar. In this case 16 parts by volume of the specialflux were used with 84 parts by volume of the tar. The tar used was arefined coke oven tar having a consistency by float test at 32 C. ofapproximately 180 seconds.

Example II.'-The gasoline used in thiscase did not sludge tar when addedby itself, but the resulting mixture was not stable and homogeneous. Thegasoline was mixed. with water gas-tar light oil in the proportion of 90parts by weight of the gasoline to 10 parts by weight of the light oil.

This special flux was added to a tar having a float test of seconds at32 C. in the proportion of 10 parts by weight of flux to parts by weightof tar, producing a mixture which was quite fluid at atmospherictemperature. The mixture was still homogeneous at the end of the eightmonths storage.

Example IlI.-The petroleum distillate used in this case was a naphthahaving an initial boiling point of 218 F. The tar used was a coke oventar having a float test of. 16'! seconds at 32 C. Upon the addition ofthe-straight naphtha to this tar the mixture became non-homogeneous in ashort time. A fiux was prepared containing 17.5 parts by weight of crudesolvent naphtha and 82.5 parts by weight of petroleum naphtha and addedto thetar in the same proportions as in Example I (16 to 84). Theresulting fluxed tar was still homogeneous after months of storage.Slightly better results were obtained by using the same proportion of acoal tar neutral oil in place of the crude solvent naphtha, although theflux composed of 10 parts by weight of the neutral oil and 90 parts byweight of the petroleum naphtha was not quite good enough to produceastable I the tar added by themselves. Thespecialfiuxes in mixed tar.'ihenuxedtarcontainingthelarger,

of the iluxed tars were composedofzlo of the individual parts by .weightof the flux-were used partsbyweight ofthetarineachcase.

was a reilned coke oven having a by weight of tar oil distillate and 90arts by non-homogeneous while theother tar containing the second naphthagstillfsatisfactory. The naphtha employed in the iiuxed tar showed alower aniline pointthan the other naphtha, the lower pointindicating ahigher proportion of compounds.

Example ,V.-A viscous distilled coke oven tar was usedas the base'inAflux composed of 80parts by weight of naphthaand20partsbyweightofneutralcoaltaroil ,pheric temperature and proved tobe stable on was added to the tar. in the of 20 parts by weight of fluxand parts by weight of tar. The iiuxed tar was quite liquid atatmosstanding for a long period of time.

Example VI.A medium consistency tar base prepared from residuum tar wasused in this case. The flux consisted of parts by weight of the samegasoline referred to-in Example II, and 10 parts by weight of water gastar light oil and l0 parts by weight of the resulting flux were usedwith 90 parts by weight of the tar. A stable and fluid fluxed tar wasproduced by. this combination.

ExampleVlL-Ihis example is given to show that by using a nu: consistingprincipally of petroleum distillates it is actually possible to effect asaving in the amount of flux used for any one purpose over that whichwould be required if the usual tar flux had been used. The same tar basewas used in each case given below but the fluxes were different asindicated. The tar base was a crude coke oven tar having an Englerspecific viscosity of 77.8 at' 50 C. and a specific gravity at 25' c. of1.171. The fluxes were added to the four tar batches in amountssuiiicient to produce viscosities' of the same order.

aoeaoso Itisimpracticaltostaterangesofproportionsoftheconstituentsofaiiusortheratiosofvari ous combinations of suchconstituents suitable forthe various'tars. Inanyins'tance,ifagivencombination-oi gasoline with aromatic hydrocab typeofthisnewflux.Coldpatchroadtarswhich.

consistofaheavydistilledtarandalightflux and also other fluxed, heavytars will prove to give more satisfactoryresultswhenprepsredusing thisnew flux. 'lheinvention willilnd application in the manufacture of coaltar paints. slthoughinthiscaseamuohsmallerpercentageofpetroleumdistillatewillhavetobeusedintheflux thanwastbecaseinthespecinc for road, tar fluxes cited above. It should benoted thahthis new flux is actually a universal flux for bituminousmaterials and as such will eliminate the necessity or keeping largestocks of diilerent types of has where diil'erent types oi iiuxedbitumens are manufactured or used. Its universal iiuxing propertiu lead.to applications "in other fields than those mentioned afive. By

employing the proper proportions and ingredientsinthisnewflux,itsusecanbeext'endedbyineluding it in a universal primerfor underground pipes, in roof coatings. roof cements and other suchmaterials.

Inviewoftheaboveitcanbeseenthatitis entirely feasible to modify thecharacteristics of petroleum distillates and similar aliphatichydrocarbon oils in the manner described herein so that they may be usedfor the iluxing of tars and tar products and that many advantages arisefrom the use of the petroleum distillates for these purposes.

Thetars or pyrogenous distillates referred to in the description of thepresent invention may be defined as blackto dark-brown bituminouscondensates which yield substantial quantities of pitch when partiallyevaporated or fractionally distilled. The pitches referred to are blackor dark-brown solid cementitious residues which gradually liquefy whenheated and which are produced by the partial evaporation or fractionaldistillation of the above tars.

What I claim is:-,

1. A composition of matter comprising a substantially homogeneous,stable. flowable, pyrogenous distillate tar product consisting ofpyrogenous distillate tar or tars selected from a group consisting ofcoke oven tar, gas-works retort tar. low temperature tar, blast furnacetar. water gas tar, and oil gas tar; and a mixing liq d containingaromatic hydrocarbon oil originating from coal tar and a preponderantproportion of aliphatic hydrocarbon oil originating from petroleum oil.

p faoeacso condition by the said aromatic hydrocarbon oil.

2. A composition of matter-comprising a substantially homogeneous,stable, flowable, pyrogenous distillate tar product consisting ofpyrog-' enous distillate tar or tars selected from a group consisting ofcoke oven tar, gas-works retort tar, low temperature tar, blast furnacetar, water gas tar, and oil gas tar; and a fluxing liquid containingaromatic hydrocarbon oil originating from coal' tar and a proportion ofgasoline greater than that of the said aromatic hydrocarbon oil, thesaid tar product being substantially free from sludge that forms whenaliphatic hydrocarbon oil alone is added to the said pyrogenousdistillate tar, and the said aromatic hydrocarbon oil being present insufficient amount to maintain the said tar product substantiallypermanently homogeneous and stable. I 1

3. A composition of matter comprising a substantially homogeneous;stable, flowable, pyrogenous distillate tar productconsisting ofpyrogenous distillate tar or tars selected from a group consisting ofcoke oven tar, gas-works retort tar, 7

tion of aliphatic hydrocarbon ofl, of the boiling .rogenous distillatetar or tars selected from a range of kerosene, greater than that of thesaid aromatic hydrocarbon oil,'the said aromatic hydrocarbon oiloriginating from coal tar, the said aliphatic hydrocarbon oiloriginating from petro-. leum oil, the said tar product beingsubstantially free from sludge that forms when aliphatic hydro carbonoil alone is' added to the said pyr genous distillate tar, and the saidaromatic hydrocarbon oil being present in sufiicient amount to maintainthe said tar product substantially permanently homogeneous and stable.

4. A composition of matter comprising a substantially homogeneous,stable, flowable, pyrogenous distillate tar' product consisting ofp'ygroup consisting'of coke oven tar, gasworlrs retort tar,low"-temperature tar,'blast furnace tar,

water gas ta'r,"and oil gastar; and a n n liquid containing a relativelylow-boili distillate of pyrogenousdistillate tar and a p rtion of arelatively low-boiling aliphatic pe roleum product greater than that ofthe said low-boiling distillate of pyrogenous distillate tar, the saidtar product being substantially free from sludge that forms whenaliphatic hydrocarbon oil alone I .is added to the said pyrogenousdistillate tar,

tially 80 C. to substantially 400 C. the major portion thereof boilingbelow 300 C.,'the said I '1- aliphatic hydrocarbon oil being present ingreater proportions thanthe said aromatic hydrocarbon oil; andpyrogenous distillate tar or tars selected from a group consisting ofcoke oven tar, gasworks retort tar, low temperature tar, blast fur nacetar, water gas tar, and oil gas tar; the said aromatic hydrocarbon oilbeingnpresent in an amount suilicient to inhibit precipitation ofconstituents of tar and suflicient to maintain the said product stableover a longer period than is possible in theabsence oi' the saidaromatic hydrocarbon oil.

6. A composition of matter comprising a stable homogeneous pyrogenousdistillate-tar product having as a flux a combination of aliphatichydrocarbon oil originating from petroleum oil and aromatic hydrocarbonoil originating from,

coal'tar, the combined oils having solvent characteristics approachingthose of aromatic oil compounds. alone, and containing a preponderantproportion of aliphatic hydrocarbon material which when added withoutthe aromatic hydrocarbon material forms an unstable; non-homogeneousproduct with pyrogenous distillate tar or tars of the group consistingof coke oven tar, gas-works retort tar, low temperature tar, blastfurnace tar, water gas tar and oil gas tar, but

which when added to such tar with the aro-. matic hydrocarbonmaterialforms a substantially permanently stable fluxed tar productsubstantially free from sludge. v 7. A composition of matter. comprisinga fluxed bituminous product containing constituents of v pitch ofpyrogenous distillate tar or tars selected from a group consisting ofcoke oven tar. gasworks retort tar, low temperature tar, blast furnacetar, water gas tar, and oil gas tar; and a 1 mixture containingaliphatichydrocarbon oil of petroleum oil, and an'aromatic hydrocarbonoil or relatively low boiling point'and originating p from coal tar, thesaid mixture containing a major proportion of the said aliphatic oil,and

the said bituminous product being substantially s free from precipitatethat forms when aliphatic hydrocarbon oil alone is added to the saidpitch. 8. A composition of matter comprising a fluxed bituminous productcontaining modified pyrogenous distillate tar or tars, the said tarortars selected from a group consisting of coke oven tar,

gas-works retort tar, low temperature tar, blast furnace tar, water gastar; andoil gas tar; and a mixture containing aliphatic hydrocarbon oilof' relatively low boiling point and originating from petroleum oil, andan aromatic hydrocarbon oil oi relatively low boiling point andoriginating from coal tar, the said mixture containing a majorproportion of the said aliphatic oil,

, and the said bituminous product being, substan-' tially free fromprecipitate that forms when aliphatic hydrocarbon oil alone-is added tothe said modified tar.

9. A composition of matter comprising a fluxed bituminous productcontaining pyrogenous distillate tar or tars selectedfrom a groupconsist ing of coke oven tar, gas-works retort-tar, vlow temperaturetar, blast furnace tar, Water gas tar,

and oil gas tar; and containing asphalt, a rela-

